CN101918459A - Improved method for producing comb polymers by adding an antioxidant, resulting polymers and uses thereof - Google Patents

Improved method for producing comb polymers by adding an antioxidant, resulting polymers and uses thereof Download PDF

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CN101918459A
CN101918459A CN2008801248416A CN200880124841A CN101918459A CN 101918459 A CN101918459 A CN 101918459A CN 2008801248416 A CN2008801248416 A CN 2008801248416A CN 200880124841 A CN200880124841 A CN 200880124841A CN 101918459 A CN101918459 A CN 101918459A
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methyl
acid
functional group
multipolymer
comb
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CN101918459B (en
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让-马克·苏奥
大卫·普拉特尔
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Coatex SAS
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    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/91—Graft copolymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2664—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers
    • C04B24/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers containing polyether side chains
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
    • C04B2103/0059—Graft (co-)polymers
    • C04B2103/006—Comb polymers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
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    • D21H17/33—Synthetic macromolecular compounds
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    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/56—Polyamines; Polyimines; Polyester-imides
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    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
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Abstract

The invention lies in the use of an antioxidant during the reaction for functionalization of a (meth)acrylic polymer in the dry state with polyoxyalkyl side groups, so as to improve the degree of grafting of the final polymer. The resulting polymers constitute another subject matter of the invention, as do the aqueous formulations which contain them.

Description

Make the improving one's methods of comb-shaped polymer, resulting polymers and application thereof by adding antioxidant
The present invention relates to the improvement of comb-shaped polymer synthetic method, this comb-shaped polymer has (methyl) propenoic acid main chain that is fixed with the polyoxyalkylated side group on it.
Known this polymkeric substance especially for based on the composition of water-setting tackiness agent in mobile, workability or reduce and give favorable properties aspect its water content.
For many years, those skilled in the art rely on four kinds of methods to prepare this polymkeric substance.Method the earliest is included in the following multipolymer that produces maleic anhydride and another hydrophobic monomer of existence of organic solvent (as toluene or methylethylketone), grafting o-alkylation side chain on this multipolymer (for example, referring to file WO 97/39037).Yet organic solvent residual is reluctant objectionable impurities.
Second kind of synthetic method comprises (methyl) Acrylic Acid Monomer and methacrylic acid polyether macromonomer copolymerization in solvent or water medium (referring to file US 2,001 001797 and FR2,861,399).In this case, the high price of initial (methyl) vinylformic acid macromonomer constitutes the obstacle of this method of enforcement.
The third synthetic method comprises the vinyl macromonomer and (methyl) Acrylic Acid Monomer copolymerization in solvent or water medium (referring to file US2004/235687) with o-alkylation side chain.As previously mentioned, the high price of initial macromonomer constitutes obstacle to those skilled in the art.
The 4th kind of synthetic method is included in the solvent medium that (referring to file FR 2,776,285) utilizes alkoxyl group poly suboxygen alkyl glycol esterification (methyl) acrylate homopolymer or multipolymer in (referring to file EP 1,016,638) or the water medium.Yet this method can not get satisfied result.
Therefore, according to the novel method of file FR 2,900,930 these comb-shaped polymers of exploitation preparation, this novel method has remedied the shortcoming of the synthetic technology of the macromonomer that adopts hazardous solvent or costliness, and obtains than passing through the higher productive rate of esterification gained in water medium.
The novel part of this method comprises with drying regime implements esterification to (methyl) acrylate homopolymer or multipolymer.More specifically, (methyl) acrylate homopolymer or multipolymer are introduced to contain with dried forms be useful in the melting media of realizing functionalized group: building-up reactions is carried out being higher than under 100 ℃ of temperature.Therefore, with respect to the same reaction of carrying out in water medium, the reaction times shortens (reaching given transformation efficiency) greatly.
In file FR 2,900,930, by measuring transformation efficiency via the titrating acid number of carboxyl functional group: titrating carboxyl functional group is unreacted functional group.This document with grafted conceptual expansion on the dry polymeric to the amidate action of alkoxyl group poly suboxygen alkyl amine and with the ethoxylation of olefin oxide.
Based on the invention that provides among the file FR 2,900,930, when utilizing methoxy poly (ethylene glycol) to come the esterification polymethyl acrylic acid, the amount of unreacted methoxy group that the applicant has used gpc measurement.Shown in the application's test #1 and #2, the value height of gained is because it equals 20 weight % of initial methoxy poly (ethylene glycol).Yet the completely dissolve of carboxyl titration method indication acid functional group: this expression esterification is complete.
As if in order to explain this result of contradiction, the applicant can determine technical problem unknown before this in this method: have secondary reaction, it is seemingly catalytic by high reaction temperature institute, and this causes the methoxyl group side chain to remove.In order to remedy this shortcoming, the applicant successfully designs and a kind of prior art is carried out improved method.
This improvement is included in before the functionalized stage and/or applies at least a antioxidant afterwards, and this can reduce the amount of the measured unreacted functional group of GPC.Thus, seek to limit very significantly the quantity of secondary oxidation reaction, this secondary oxidation reaction causes removing of side chain: the result improves the productive rate of reaction greatly.Antioxidant is meant the material with restriction molecule cracking and/or free radical growing ability.
Except the technique effect of the highly significant relevant with applying this antioxidant, creativeness of the present invention also has been to upgrade previous unknown technical problem in the currently known methods: side chain removes from comb-shaped polymer under temperature action.Then, in order to address this problem, the applicant has successfully improved the basic skills of prior art, because this can make those skilled in the art get around harmful technology (solvent) and/or expensive technology (initial macromonomer).Therefore, those skilled in the art can select with low-cost, do not use solvent, fast and the mode of high yield prepare comb-shaped polymer with (methyl) propenoic acid main chain that is fixed with the polyoxyalkylated side group on it.
Thus, first purpose of the present invention is that a kind of preparation has the method for the comb-shaped polymer of (methyl) propenoic acid main chain and polyoxyalkylated side group, and this method comprises:
A) preparation contains the solution of the one at least in (methyl) acrylate homopolymer and/or (methyl) vinylformic acid and at least a other monomeric multipolymer,
B) solution that obtains in a) of drying step, so that obtain (methyl) acrylate homopolymer and/or (methyl) vinylformic acid and at least a other monomeric multipolymer of drying regime,
C) at least a alkoxyl group poly suboxygen alkyl amine of at least a alkoxyl group poly suboxygen alkyl glycol of the product of the drying regime that will obtain according to step b) and molten state and/or molten state and/or liquid state or at least a olefin oxide of gasiform mix,
D) make described (methyl) acrylate homopolymer and/or multipolymer functionalized by following reaction:
-with the esterification of at least a alkoxyl group poly suboxygen alkyl glycol,
-and/or with the amidate action of at least a alkoxyl group poly suboxygen alkyl amine,
-or with the ethoxylation of at least a olefin oxide,
And, it is characterized in that, during step a) and/or step b) and/or step c), add antioxidant.
According to first preferred variant of the present invention, described antioxidant is the amine with at least one aryl that is replaced by alkyl chain, described amine preferably has two aryl, wherein at least one aryl is had the alkyl chain replacement of 3-9 carbon atom, and more preferably the CAS of this compound is numbered 68411-46-1.CIBA TMThe Irganox that company sells TMThe 5057th, the commercial embodiments of this compound.
According to second preferred variant of the present invention, described antioxidant is an organophosphorus compounds, is preferably aromatics and/or aliphatic phosphites, more preferably is selected from the compound that CAS is numbered 25550-98-5 and 101-02-0.DOVER TMThe Doverphos that company sells TM7 and Doverphos TMThe 10th, the commercial embodiments of this compound.
The applicant is stressed that the creativeness of these two preferred variant specifically obtains the support of the following fact: Irganox TM5057 and Doverphos TM7 and Doverphos TMUp to the present 10 just be applied to stabilizing polyurethane foams and polyester respectively in very different technical fields.
The feature of the inventive method also is, step c) is carried out under 150 ℃-250 ℃, preferred 180 ℃-220 ℃ temperature.
The feature of the inventive method is that also step c) is carried out in the presence of catalyzer, described catalyzer is preferably selected from tosic acid and lithium hydroxide.
The feature of the inventive method is that also described alkoxyl group poly suboxygen alkyl glycol is a methoxyl group poly suboxygen alkyl glycol, is preferably methoxy poly (ethylene glycol).
The feature of the inventive method is that also described alkoxyl group poly suboxygen alkyl amine is methoxyl group poly suboxygen alkyl amine, is preferably methoxyl group poly suboxygen ethylamine.
The feature of the inventive method is that also described olefin oxide is ethylene oxide or propylene oxide or its mixture.
The feature of the inventive method also is, described (methyl) acrylate homopolymer and/or multipolymer are by in the presence of catalyst system and chain-transfer agent, in the suspensoid or precipitation of correct solvent, solution free radical polymerization method in direct or inverted emulsion, or pass through controlled free radical polymerization process, preferably pass through the polymerization process of (NMP) or cobalt-oxime mediation of nitrogen oxygen mediation, by atom transfer radical polymerization method (ATRP), or obtain by the free radical polymerisation process that adds sulfur derivatives mediation, described derivative is selected from carbamate, two thioesters or trithiocarbonate (RAFT) or xanthate.
The feature of the inventive method is that also other monomer of described (methyl) acrylic copolymer is selected from following monomer or these monomeric mixtures:
-at least a unsaturated the anionic monomer of vinyl with mono carboxylic functional group is preferably acrylic or methacrylic acid or its mixture,
-at least a ethylenically unsaturated monomer, be selected from least a ethylenically unsaturated monomer with dicarboxyl functional group, be preferably selected from Ba Dousuan, methylene-succinic acid or toxilic acid, perhaps be selected from carboxylic acid anhydride, preferred maleic anhydride, perhaps be selected from ethylenically unsaturated monomer with sulfo group functional group, and be preferably selected from 2-acrylamido-2-methyl-propane-sulfonic acid, vinyl sulfonic acid or allyl ethers sulfonate, styrene sulfonate, or be selected from ethylenically unsaturated monomer with phosphoric acid functional group, be preferably selected from vinyl phosphoric acid, methacrylic acid phosphoric acid glycol ester, methacrylic acid propanediol phosphate ester, vinylformic acid phosphoric acid glycol ester, vinylformic acid propanediol phosphate ester and their ethoxylate, or be selected from ethylenically unsaturated monomer with phosphonic acid functional groups, be preferably vinyl phosphonate, or be selected from vinyl caprolactone or vinyl pyrrolidone or its mixture
-at least a water-insoluble monomer, for example alkyl acrylate or alkyl methacrylate or its mixture.
The feature of the inventive method also is, is undertaken by atomization in moisture eliminator according to described (methyl) acrylate homopolymer of step b) enforcement and/or the drying of multipolymer.Yet those skilled in the art can utilize own known all dry technologies, with dry described homopolymer and/or multipolymer in the step b) process.
The feature of the inventive method also is, proceed to the realization content levels greater than 80% of described homopolymer and/or described multipolymer weight according to described (methyl) acrylate homopolymer of step b) enforcement and/or the drying of multipolymer, be preferably greater than 90%, more preferably greater than 95%, by METTLER-TOLEDO TMCompany measures with the halogen moisture content tester that trade(brand)name HR83 sells, and this measurement reaches 30 seconds and weightlessly carries out less than 1mg by being dried under 150 ℃.
The feature of the inventive method also is, described method is included in the optional step e that carries out after the step d)), step e) comprises that the product that obtains when step d) finished places the aqueous solution, utilizes one or more to plant neutralizing agents with the randomly neutralization completely or partially of described product then.
The feature of the inventive method also is, described neutralizing agent is selected to has in the monovalence and the neutralizing agent of functional group, be preferably selected from base cations, more preferably be selected from sodium, potassium, lithium and ammonium, or be preferably selected from primary, the second month in a season or uncle's fatty amine and/or cyclammonium, more preferably be selected from Stearyl Amine, thanomin is (single, two, trolamine), list and diethylamine, hexahydroaniline, methyl cyclohexylamine, amino-methyl propyl alcohol and morpholine, perhaps be selected from and have in the divalence and the neutralizing agent of functional group, be preferably selected from the divalence alkaline earth cation, more preferably be selected from magnesium, calcium and zinc, perhaps be selected from and have in the trivalent and the neutralizing agent of functional group, preferred aluminium, perhaps be selected from and have, perhaps be selected from their mixture more than in tervalent and the neutralizing agent of functional group.
Second purpose of the present invention is a kind of comb-shaped polymer of drying regime, this polymkeric substance has (methyl) propenoic acid main chain and grafting polyoxyalkylated side group, it is characterized in that, the percentage of grafting of the described polymkeric substance by gpc measurement is greater than 70%, be preferably greater than 80%, more preferably greater than 90%.Certainly, these polymkeric substance are by aforesaid method (certainly, not have enforcement to be placed on optional step e in the aqueous solution)) polymkeric substance that obtains.
The feature of the comb-shaped polymer of this drying regime is that also the dried solids content of described polymkeric substance is preferably greater than 85% greater than 80% of described comb-shaped polymer weight, more preferably greater than 90%, most preferably greater than 95%, by METTLER-TOLEDO TMCompany measures with the halogen moisture content tester that trade(brand)name HR83 sells, and this measurement is carried out less than 1mg until reaching 30 seconds weightlessness by dry under 150 ℃.
The 3rd purpose of the present invention is a kind of comb-shaped polymer of aqueous solution state, and described polymkeric substance has (methyl) propenoic acid main chain and grafting polyoxyalkylated side group, it is characterized in that, the percentage of grafting of described polymkeric substance is greater than 70%, be preferably greater than 80%,, pass through gpc measurement more preferably greater than 90%.Certainly, these polymkeric substance are by aforesaid method (comprising the optional step e that implements to be placed in the aqueous solution)) polymkeric substance that obtains.
The 4th purpose of the present invention is a kind of preparation that contains organic/inorganic substance or organic materials, it is characterized in that, described preparation comprises at least a comb-shaped polymer of the present invention.
The feature of these preparations also is, described preparation is the aqueous formulation that contains organic/inorganic substance or organic materials, described preparation is selected from the water dispersion or the suspensoid of inorganics or organic materials, optional dispersion agent and/or grinding aid and/or anti-sedimentation agent and/or the thickening material of comprising, or based on the waterborne compositions of water-setting tackiness agent, and be preferably concrete, mortar, slag, grout, plaster or paper coating or paint or makeup or detergent formulations or fabric preparation or ceramic preparation or drilling well slurry.
Following examples content that the present invention may be better understood, but do not limit its scope.
Embodiment
In all embodiment of the application, calculate esterification yield by following the trail of acid number, this can determine the ratio of unreacted acid functional group (according to file FR 2,900,930 described methods) still.
The molecular weight of prepared comb-shaped polymer and not the content of grafted methoxy poly (ethylene glycol) all by utilizing the gpc measurement of following method.
Chromatographic system is by Waters TM717 automatic samplers, ERC 3112 online de-aerators, Waters 515HPLC pump, post stove, Waters TM2410 refractometers, Viscotek TMT60A scattering of light viscosimetric analysis detector, Ultrahydrogel Waters TMGuard column, linear Waters TMUltrahydrogel post+2 a Waters Ultrahydrogel 120 post (length 30cm; Diameter 7.8mm) and the computer system with TriSEC 3.0 softwares form.Mobile phase is prepared by the filtering 666mM sodium sulfate of 0.1 μ m mother liquor.This solution with 10% mixes with 5% CAN qsp ultrapure water, is neutralized to pH 9 with sodium hydroxide.Flow is 0.8mL/ minute, and the temperature of post and refractometer is 30 ℃, and the sensitivity of refractometer and scaling factor equal 4 and 20 respectively.Sample has 4mg sec product/ml mobile phase.They filter through 0.2 μ m before injection.Volume injected is 100 μ l, and be 50 minutes analysis time.Utilization has the gauged PEO 21k Viscotek of flowing TMMain frame is calibrated negative water peak value and T70K dextran.
Embodiment 1
This embodiment illustrates 2,900, the 930 described art methods as file FR, does not wherein apply any antioxidant.
Begin is to obtain by COATEX TMCompany is with the aqueous solution of 30 quality % of the methacrylic acid homo thing of trade(brand)name TP 941 sales.Dry then this solution.Be placed on temperature and be in 85 ℃ the preheating chamber.Utilize nozzle that product is injected in the spray chamber of spray-dryer under the pressure of 60 crust.And 300 ℃ warm airs are injected in the spray chamber, and this causes the water flash distillation in the polymers soln.This exsiccant yield is greater than 99%, and the dry polymeric quality that promptly obtains after the drying equals 99% of contained polymer quality in the initial aqueous solution at least.
The temperature of the polymkeric substance of discharging equals 50 ℃.
This drying operation is extremely quick, because it only continues several seconds.Then, reclaim the polymkeric substance of dry powder.
Test No. 1
Then, in being furnished with 0.25 liter of glass reactor of mechanical stirring and electric heater, mix:
The methoxy poly (ethylene glycol) of-80g (or 0.04 mole) fusion form, its molecular weight equals the 2000g/ mole, by CLARIANT TMCompany is with trade(brand)name Polyglykol TMM2000 sells,
-0.24g lithium hydroxide,
The dry methylene acrylate homopolymer of-13.8g (or 0.16 mole of methacrylic acid), it obtains by above-mentioned drying means.
Carry out the esterification of methacrylic acid homo thing and methoxy poly (ethylene glycol) then.Subsequently, by nitrogen gas stream whole associated plant was outgased 20 minutes.When stirring, be warming up to 190 ℃ gradually, and whole associated plant is placed vacuum (20mm mercury column), wherein this temperature-rise period is 60 minutes consuming time.Then, with this mixture 190 ℃ of following thermal treatments 120 minutes.Then, dilute with this associated plant cooling and with 78.3g water, the sodium hydroxide of following with 50% is neutralized to pH 8.4.
Before esterification, the acid number (IA of mixture i) equal 83mg salt of wormwood/g product.After the esterification, this value (IA f) equal 34mg salt of wormwood/g product.This result is the total flow of the alcohol functional group of being added.Obtain the molecular weight of 155600g/ mole.Unreacted methoxy poly (ethylene glycol) content equals 20 weight % of initial methoxyl group or the actual grafted methoxyl group productive rate that calculates equals 57 weight % of initial methoxyl group.
Test No. 2
Then, in being furnished with 0.25 liter of glass reactor of mechanical stirring and electric heater, mix:
The Polyglykol of-80g (or 0.04 mole) TMM 2000,
-1.9g tosic acid,
The dry methylene acrylate homopolymer of-13.8g (or 0.16 mole of methacrylic acid), it obtains by above-mentioned drying means.
Carry out the esterification of methacrylic acid homo thing and methoxy poly (ethylene glycol) then.Subsequently, by nitrogen gas stream whole associated plant was outgased 20 minutes.When stirring, be warming up to 190 ℃ gradually, and whole associated plant is placed vacuum (20mm mercury column), wherein this temperature-rise period is 60 minutes consuming time.Then, with this mixture 190 ℃ of following thermal treatments 120 minutes.Then, dilute with this associated plant cooling and with 78.3g water, the sodium hydroxide of following with 50% is neutralized to pH 8.4.
Before esterification, the acid number (IA of mixture i) equal 83mg salt of wormwood/g product.After the esterification, it equals 35mg salt of wormwood/g product.This result is the total flow of the alcohol functional group of being added.Obtain the molecular weight of 201100g/ mole.Unreacted methoxy poly (ethylene glycol) content equals 20.5 weight % of initial methoxyl group or the actual grafted methoxyl group productive rate that calculates equals 55.5 weight % of initial methoxyl group.
These results clearly illustrate that, are considering under the situation that acid functional group disappears, and the high temperature direct esterification reaction of implementing polymethyl acrylic acid has high yield.On the other hand, high-load free polyoxyethylene glycol shows methoxyl group and unstable under this temperature, thereby this causes thermal destruction to produce removing of side chain.
Embodiment 2
This embodiment illustrates the present invention, promptly applies oxidation inhibitor in as file FR 2,900,930 described methods.
Test #3 to #9 separately all process in accordance with the present invention a) and b) obtain methacrylic acid homo thing solution and be dried, wherein experimental program is with to test 1 and 2 identical.
Test No. 3
According to the step c) of the inventive method, in being furnished with 0.25 liter of glass reactor of mechanical stirring and electric heater, mix:
The Polyglykol of-80g TMM 2000,
-0.24g lithium hydroxide,
The dry methylene acrylate homopolymer of-13.8g (or 0.16 mole of methacrylic acid), it obtains by above-mentioned drying means.
-0.20g CIBA TMThe Irganox that company sells TM5057.
Process in accordance with the present invention d), carry out esterification.Subsequently, by nitrogen gas stream whole associated plant was outgased 20 minutes.When stirring, be warming up to 190 ℃ gradually, and whole associated plant is placed vacuum (20mm mercury column), wherein this temperature-rise period is 60 minutes consuming time.Then, with this mixture 190 ℃ of following thermal treatments 120 minutes.Then, dilute with this associated plant cooling and with 128g water, the sodium hydroxide of following with 50% is neutralized to pH 8.4.
Test No. 4
According to the step c) of the inventive method, in being furnished with 0.25 liter of glass reactor of mechanical stirring and electric heater, mix:
The Polyglykol of the fusion form of-36.1g TMM 2000,
-0.24g lithium hydroxide,
The dry methylene acrylate homopolymer of-15.68g, it obtains by above-mentioned drying means,
The Irganox of-0.18g TM5057.
Process in accordance with the present invention d), carry out esterification.Subsequently, by nitrogen gas stream whole associated plant was outgased 20 minutes.When stirring, be warming up to 210 ℃ gradually, and whole associated plant is placed vacuum (20mm mercury column), wherein this temperature-rise period is 60 minutes consuming time.Then, with this mixture 210 ℃ of following thermal treatments 30 minutes.Then, dilute with this associated plant cooling and with 78.3g water, the sodium hydroxide of following with 50% is neutralized to pH 8.4.
Test No. 5
According to the step c) of the inventive method, in being furnished with 0.25 liter of glass reactor of mechanical stirring and electric heater, mix:
The Polyglykol of the fusion form of-52.1g TMM 2000,
-0.24g lithium hydroxide,
The dry methylene acrylate homopolymer of-15g, it obtains by above-mentioned drying means,
The Irganox of-0.2g TM5057.
Process in accordance with the present invention d), carry out esterification.Subsequently, by nitrogen gas stream whole associated plant was outgased 20 minutes.When stirring, be warming up to 210 ℃ gradually, and whole associated plant is placed vacuum (20mm mercury column), wherein this temperature-rise period is 45 minutes consuming time.Then, with this mixture 210 ℃ of following thermal treatments 30 minutes.Then, dilute with this associated plant cooling and with 105g water, the sodium hydroxide of following with 50% is neutralized to pH 8.4.
Test No. 6
According to the step c) of the inventive method, in being furnished with 0.25 liter of glass reactor of mechanical stirring and electric heater, mix:
The Polyglykol of the fusion form of-44.1g TMM 2000,
-0.24g lithium hydroxide,
The dry methylene acrylate homopolymer of-15.34g, it obtains by above-mentioned drying means,
The Irganox of-0.2g TM5057.
Process in accordance with the present invention d), carry out esterification.Subsequently, by nitrogen gas stream whole associated plant was outgased 20 minutes.When stirring, be warming up to 210 ℃ gradually, and whole associated plant is placed vacuum (20mm mercury column), wherein this temperature-rise period is 45 minutes consuming time.Then, with this mixture 210 ℃ of following thermal treatments 60 minutes.Then, dilute with this associated plant cooling and with 89.8g water, the sodium hydroxide of following with 50% is neutralized to pH 8.4.
Test No. 7
According to the step c) of the inventive method, in being furnished with 0.25 liter of glass reactor of mechanical stirring and electric heater, mix:
The Polyglykol of the fusion form of-80g TMM 2000,
-1.9g tosic acid,
The dry methylene acrylate homopolymer of-13.8g, it obtains by above-mentioned drying means,
The Irganox of-0.20g TM5057.
Process in accordance with the present invention d), carry out esterification.Subsequently, by nitrogen gas stream whole associated plant was outgased 20 minutes.When stirring, be warming up to 190 ℃ gradually, and whole associated plant is placed vacuum (20mm mercury column), wherein this temperature-rise period is 60 minutes consuming time.Then, with this mixture 190 ℃ of following thermal treatments 120 minutes.Then, dilute with this associated plant cooling and with 128g water, the sodium hydroxide of following with 50% is neutralized to pH 8.4.
Test No. 8
According to the step c) of the inventive method, in being furnished with 0.25 liter of glass reactor of mechanical stirring and electric heater, mix:
The Polyglykol of the fusion form of-80g TMM 2000,
-0.24g lithium hydroxide,
The dry methylene acrylate homopolymer of-13.8g, it obtains by above-mentioned drying means,
The DOVER CHEMICAL of-0.20g TMThe Doverphos that company sells TM7.
Process in accordance with the present invention d), carry out esterification.Subsequently, by nitrogen gas stream whole associated plant was outgased 20 minutes.When stirring, be warming up to 210 ℃ gradually, and whole associated plant is placed vacuum (20mm mercury column), wherein this temperature-rise period is 60 minutes consuming time.Then, with this mixture 210 ℃ of following thermal treatments 30 minutes.Then, dilute with this associated plant cooling and with 128g water, the sodium hydroxide of following with 50% is neutralized to pH 8.4.
Test No. 9
According to the step c) of the inventive method, in being furnished with 0.25 liter of glass reactor of mechanical stirring and electric heater, mix:
The CLARIANT of the fusion form of-80g TMThe Polyglykol that company sells TMM 2000,
-0.24g lithium hydroxide,
The dry methylene acrylate homopolymer of-13.8g, it obtains by above-mentioned drying means,
The DOVER CHEMICAL of-0.20g TMThe Doverphos that company sells TM10.
Process in accordance with the present invention d), carry out esterification.Subsequently, by nitrogen gas stream whole associated plant was outgased 20 minutes.When stirring, be warming up to 210 ℃ gradually, and whole associated plant is placed vacuum (20mm mercury column), wherein this temperature-rise period is 60 minutes consuming time.Then, with this mixture 210 ℃ of following thermal treatments 30 minutes.Then, dilute with this associated plant cooling and with 128g water, the sodium hydroxide of following with 50% is neutralized to pH 8.4.
Gained the results are shown in the table 1.
Table 1
Test No. 1 2 3 4 5
Prior art (PA)/the present invention (IN) PA PA IN IN IN
?IA i(mg KOH/ mg polymkeric substance) 83 83 86 188 140
?IA f(mg KOH/ mg polymkeric substance) 34 35 30 130 70
Mw (g/ mole) 155600 198000 73950 51200 64400
Percentage of grafting (grafting of % methoxyl group) 57 56 79 91 86
Test No. 6 7 8 9
Prior art (PA)/the present invention (IN) IN IN IN IN
?IA i(mg KOH/mg polymkeric substance) 160 86 86 86
?IA f(mg KOH/mg polymkeric substance) 80 30 30 30
Mw (g/ mole) 61400 69200 78100 63400
Percentage of grafting (grafting of % methoxyl group) 91 90 96 95
These results clearly illustrate that if consider the disappearance of acid functional group, then the high temperature direct esterification of polymethyl acrylic acid is carried out with high yield.On the other hand, as the high molecular of final polymkeric substance, high-load free poly suboxygen ethyl shows that methoxyl group poly suboxygen ethyl is unstable under the acid-functionalized temperature of polymethyl.This causes the thermal destruction of comb-shaped polymer, produces removing of poly suboxygen ethyl side chains.
On the contrary, apply antioxidant and can obtain the lower and poly suboxygen ethyl content of molecular weight than lower graftomer in the test 1 and 3, but keep the replacement degree of being on close level with carboxyl functional group: therefore, the productive rate of art methods is significantly improved.

Claims (19)

1. method for preparing the comb-shaped polymer with (methyl) propenoic acid main chain and polyoxyalkylated side group comprises:
A) preparation contains the solution of the one at least in (methyl) acrylate homopolymer and/or (methyl) vinylformic acid and at least a other monomeric multipolymer,
B) solution that obtains in a) of drying step, so that obtain (methyl) acrylate homopolymer and/or (methyl) vinylformic acid and at least a other monomeric multipolymer of drying regime,
C) at least a alkoxyl group poly suboxygen alkyl amine of at least a alkoxyl group poly suboxygen alkyl glycol of the product of the drying regime that will obtain according to step b) and molten state and/or molten state and/or liquid state or at least a olefin oxide of gasiform mix,
D) make described (methyl) acrylate homopolymer and/or multipolymer functionalized by following reaction:
-with the esterification of at least a alkoxyl group poly suboxygen alkyl glycol,
-and/or with the amidate action of at least a alkoxyl group poly suboxygen alkyl amine,
-or with the ethoxylation of at least a olefin oxide,
It is characterized in that, during step a) and/or step b) and/or step c), add antioxidant.
2. method according to claim 1, it is characterized in that, described antioxidant is the amine with at least one aryl that is replaced by alkyl chain, described amine preferably has two aryl, wherein at least one aryl is had the alkyl chain replacement of 3-9 carbon atom, and more preferably the CAS of this compound is numbered 68411-46-1.
3. method according to claim 1 is characterized in that described antioxidant is an organophosphorus compounds, is preferably aromatics and/or aliphatic phosphites, more preferably is selected from the compound that CAS is numbered 25550-98-5 and 101-02-0.
4. according to each described method among the claim 1-3, it is characterized in that step c) is carried out under 150 ℃-250 ℃, preferred 180 ℃-220 ℃ temperature.
5. according to each described method in the claim 1～4, it is characterized in that step c) is carried out in the presence of catalyzer, described catalyzer is preferably selected from tosic acid and lithium hydroxide.
6. according to each described method in the claim 1～5, it is characterized in that described alkoxyl group poly suboxygen alkyl glycol is a methoxyl group poly suboxygen alkyl glycol, is preferably methoxy poly (ethylene glycol).
7. according to each described method in the claim 1～5, it is characterized in that described alkoxyl group poly suboxygen alkyl amine is methoxyl group poly suboxygen alkyl amine, is preferably methoxyl group poly suboxygen ethylamine.
8. according to each described method in the claim 1～5, it is characterized in that described olefin oxide is ethylene oxide or propylene oxide or its mixture.
9. according to each described method among the claim 1-8, it is characterized in that, described (methyl) acrylate homopolymer and/or multipolymer are by in the presence of catalyst system and chain-transfer agent, solution free radical polymerization method in direct emulsion, perhaps pass through controlled free radical polymerization process, preferably by nitroxyl free radical mediation or cobalt-oxime free radical mediated polymerization (NMP) method, by atom transfer radical polymerization method (ATRP), or obtain by the free radical polymerisation process that adds sulfur derivatives mediation, described derivative is selected from carbamate, two thioesters or trithiocarbonate (RAFT) or xanthate.
10. according to each described method among the claim 1-9, it is characterized in that other monomer of described (methyl) acrylic copolymer is selected from following monomer or these monomeric mixtures:
-at least a unsaturated the anionic monomer of vinyl with mono carboxylic functional group is preferably acrylic or methacrylic acid or its mixture,
-at least a ethylenically unsaturated monomer, be selected from least a ethylenically unsaturated monomer with dicarboxyl functional group, be preferably selected from Ba Dousuan, methylene-succinic acid or toxilic acid, perhaps be selected from carboxylic acid anhydride, preferred maleic anhydride, perhaps be selected from ethylenically unsaturated monomer with sulfo group functional group, and be preferably selected from 2-acrylamido-2-methyl-propane-sulfonic acid, vinyl sulfonic acid or allyl ethers sulfonate, styrene sulfonate, or be selected from ethylenically unsaturated monomer with phosphoric acid functional group, be preferably selected from vinyl phosphoric acid, methacrylic acid phosphoric acid glycol ester, methacrylic acid propanediol phosphate ester, vinylformic acid phosphoric acid glycol ester, vinylformic acid propanediol phosphate ester and their ethoxylate, or be selected from ethylenically unsaturated monomer with phosphonic acid functional groups, be preferably vinyl phosphonate, or be selected from vinyl caprolactone or vinyl pyrrolidone or its mixture
-at least a water-insoluble monomer, for example alkyl acrylate or alkyl methacrylate or its mixture.
11., it is characterized in that described (methyl) acrylate homopolymer of implementing according to step b) and/or the drying of multipolymer are undertaken by atomization according to each method among the claim 1-10 in moisture eliminator.
12. according to each method among the claim 1-11, it is characterized in that, proceed to the realization content levels greater than 80% of described homopolymer and/or described multipolymer weight according to described (methyl) acrylate homopolymer of step b) enforcement and/or the drying of multipolymer, be preferably greater than 90%, more preferably greater than 95%, by by METTLER-TOLEDO TMCompany measures with the halogen moisture content tester that trade(brand)name HR83 sells, and this measurement reaches 30 seconds and weightlessly carries out less than 1mg by being dried under 150 ℃.
13. according to each method among the claim 1-12, it is characterized in that, described method is included in the optional step e that carries out after the step d)), step e) comprises that the product that obtains when step d) finished places the aqueous solution, utilizes one or more to plant neutralizing agents with the randomly neutralization completely or partially of described product then.
14. method according to claim 13, it is characterized in that, described neutralizing agent is selected to has in the monovalence and the neutralizing agent of functional group, be preferably selected from base cations, more preferably be selected from sodium, potassium, lithium and ammonium, or be preferably selected from primary, the second month in a season or uncle's fatty amine and/or cyclammonium, more preferably be selected from Stearyl Amine, thanomin is (single, two, trolamine), list and diethylamine, hexahydroaniline, methyl cyclohexylamine, amino-methyl propyl alcohol and morpholine, perhaps be selected from and have in the divalence and the neutralizing agent of functional group, be preferably selected from the divalence alkaline earth cation, more preferably be selected from magnesium, calcium and zinc, perhaps be selected from and have in the trivalent and the neutralizing agent of functional group, preferred aluminium perhaps is selected from and has more than in tervalent and the neutralizing agent of functional group, perhaps is selected from their mixture.
15. comb-shaped polymer by obtaining according to each described method among the claim 1-12, described polymkeric substance has (methyl) propenoic acid main chain and grafted polyoxyalkylated side group, it is characterized in that, the percentage of grafting of described polymkeric substance is greater than 70%, be preferably greater than 80%, more preferably greater than 90%, pass through gpc measurement.
16. the comb-shaped polymer of drying regime according to claim 15 is characterized in that, the dried solids content of described polymkeric substance is greater than 80% of described comb-shaped polymer weight, be preferably greater than 85%, more preferably greater than 90%, most preferably greater than 95%, by by METTLER-TOLEDO TMCompany measures with the halogen moisture content tester that trade(brand)name HR83 sells, and this measurement is carried out less than 1mg until 30 seconds weightlessness by dry under 150 ℃.
17. comb-shaped polymer by the aqueous solution state that obtains according to each described method among the claim 1-14, described polymkeric substance has (methyl) propenoic acid main chain and grafting polyoxyalkylated side group, it is characterized in that, the percentage of grafting of described polymkeric substance is greater than 70%, be preferably greater than 80%, more preferably greater than 90%, pass through gpc measurement.
18. a preparation that contains organic/inorganic substance or organic materials is characterized in that, described preparation comprises at least a according to each described comb-shaped polymer among the claim 15-17.
19. preparation according to claim 18, it is characterized in that, described preparation is the aqueous formulation that contains organic/inorganic substance or organic materials, described preparation is selected from the water dispersion or the suspensoid of inorganics or organic materials, optional dispersion agent and/or grinding aid and/or anti-sedimentation agent and/or the thickening material of comprising, or based on the waterborne compositions of water-setting tackiness agent, and be preferably concrete, mortar, slag, grout, plaster or paper coating or paint or makeup or detergent formulations or fabric preparation or ceramic preparation or drilling well slurry.
CN2008801248416A 2008-01-17 2008-12-11 Improved method for producing comb polymers by adding an antioxidant, resulting polymers and uses thereof Expired - Fee Related CN101918459B (en)

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